US2606162A - Compositions comprising polyisocyanate modified polyesters and vinyl chloride polymers - Google Patents
Compositions comprising polyisocyanate modified polyesters and vinyl chloride polymers Download PDFInfo
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- US2606162A US2606162A US72552A US7255249A US2606162A US 2606162 A US2606162 A US 2606162A US 72552 A US72552 A US 72552A US 7255249 A US7255249 A US 7255249A US 2606162 A US2606162 A US 2606162A
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- 239000000203 mixture Substances 0.000 title claims description 51
- 229920000728 polyester Polymers 0.000 title claims description 40
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 10
- 229920000642 polymer Polymers 0.000 title claims description 8
- 239000005056 polyisocyanate Substances 0.000 title description 19
- 229920001228 polyisocyanate Polymers 0.000 title description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- 239000004800 polyvinyl chloride Substances 0.000 claims description 19
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 24
- -1 dimethyl phenyl Chemical group 0.000 description 22
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 230000009975 flexible effect Effects 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229940116351 sebacate Drugs 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 229960000250 adipic acid Drugs 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 5
- VGHCVSPDKSEROA-UHFFFAOYSA-N 2-methyl-1,4-dioxecane-5,10-dione Chemical compound CC1COC(=O)CCCCC(=O)O1 VGHCVSPDKSEROA-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 229940070765 laurate Drugs 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAALZGOZEUHCET-UHFFFAOYSA-N 1,4-dioxecane-5,10-dione Chemical class O=C1CCCCC(=O)OCCO1 PAALZGOZEUHCET-UHFFFAOYSA-N 0.000 description 2
- 229940114069 12-hydroxystearate Drugs 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013080 microcrystalline material Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- OXTNCQMOKLOUAM-UHFFFAOYSA-N 3-Oxoglutaric acid Chemical compound OC(=O)CC(=O)CC(O)=O OXTNCQMOKLOUAM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001665400 Coracias abyssinicus Species 0.000 description 1
- 241000023813 Isia Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- WWEXBGFSEVKZNE-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC2=CC=CC=C21 Chemical class N=C=O.N=C=O.C1=CC=CC2=CC=CC=C21 WWEXBGFSEVKZNE-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical group C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940072106 hydroxystearate Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 235000015250 liver sausages Nutrition 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
Definitions
- compositions co-mprising polymeric materials more particularly to compositions comprising organic polyisocyanate modified polyesters in admixture with polyvinyl chloride, and to articles and other compositions made therefrom.
- compositions comprising organic polyisocyanate modified polyester in uniform admixture with polyvinyl chloride.
- the polyisocyanate modified polyester has the properties of an excellent plasticizer and is of particular advantage because it does not readily volatilise or migrate from the compositions.
- the polyisocyanate modified polyesters show considerable advantage over the unmodified polyesters in that they are much more readily mixed into the polyvinvyl chloride, and in that any tendency to separate from or bleed out of the compositions i either very much less or completely absent.
- compositions wherein the organic polyisocyanate modified polyester has an excellent plasticising efiect on the polyvinyl chloride are those wherein from 20 to 100 parts by weight of modified polyester are used per 100 parts of polyvinyl chloride.
- the polyvinyl chloride may housed in the form of an interpolymer of vinyl chloride with one or more other compounds of polymerisable olefinic nature which is or are not used in preponderate ing amount, for example, other vinyl esters such as vinyl acetate, unsymmetrical dichloroethylene, styrene, and the esters, nitriles and amides of acrylic; methacrylic, f'umaric and maleic acids.
- other vinyl esters such as vinyl acetate, unsymmetrical dichloroethylene, styrene, and the esters, nitriles and amides of acrylic; methacrylic, f'umaric and maleic acids.
- the polyester may be formed conveniently by heating the selected reactants at polymerizing temperatures in the absence of air or oxygen under conditions whereby water is removed from the reaction. mixture in any conventional manner.
- the polyester is formed from a glycol and a dibasic carboxylic acid or an esterforming derivative of either or both of these or a mixture of two ore more of such components. If desired, a proportion of a monobasic car-'- boxylic acid or an ester-forming derivative thereof be included among the reactants.
- glycol-s examples are ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1:12-octadecanediol and pentaglycol.
- dibasic carboxylic acids are malonic, succinic, glutaric, adipic, p-xnethyl- 2 Claims. (Cl.260--22) adipic, pimelic, suberic, azelaic, sebacic, undeca-nedioic, brassylic, isophthalic, hexahydroterephthali'c, p-phenylene-diaceticand acetonedicarboxylic acid;
- the polyesters used have a molecular weight of 1000 or more. Molecular weight is usually determined by analysing the end groups of the polyesters, and by calculation from the results thereof.
- the polyesters are modified with the organic polyisocyanate in known manner, for example, by mixing them by stirring, milling or kneading, with the organic polyisocyanate and then heating the mixture, for example, at a temperature of mil-200 C. for a period of 10. to 720 minutes. Up to 15%, usually at least 3% by weight of the pclyisocyanate is used.
- a factor which influences the choice of the quantity of: the organic polyisocyanate- is the molecular weight of the final product, i. e. the organic polyisocyanate modified polyester.
- the molecular weight of the organic polyisocyanate modified polyester isgreater than10,00(), and a sufficiency of the polyisocyanate is used to allow the formation of a final product of this molecular weight.
- An indi cation of the molecular weight' may be obtained by measurement of intrinsic viscosity, and those modified polyesters having intrinsic viscosities in chloroform of 0.6 or more may be taken as conforming to the molecular weight requirement mentioned above.
- useful compositions have been obtained from organic polyisocyanate modified polyesters which are not soluble in .501- vents such as chloroform, and viscosity measurements have not been made on these.
- organic polyisocyanates examples include ethylene diisocyanate, trimethylene diisocyanate, tetramethylen diisocyanate, ,hexamethylene diisocyanate, decamethylene diisocyanate, p-phenylenediisccyanate, m-phenylene diisocyanate,
- naphthalene diisocyanates benzene l:3:5-tri-.
- organic polyisocyanate modified polyester or a mixture of more than one such modified polyester may be brought into uniform admixture with the polyvinyl chloride in a number of ways.
- the components may be mixed or milled together, if desired, at a moderately elevated temperature, as such or in the presence of organic liquids, for example, nitroparafiins, chloroform, ethylene dichloride, benzene I and mixtures of ethyl acetate with ethylene dichloride which are solvents or swelling agents for one or both of the components; the organic liquids may be removed as and when convenient.
- solutions of the components may be mixed.
- the organic polyisocyanate modified polyester may be formed in situ, as by incorporating the polyester or mixture of polyesters with the polyvinyl chloride and by also incorporating with such mixture an organic polyisccyanate or mixture of organic polyisocyanates, and thereafter subjecting the composition to a heating operation whereby the modified polyester or mixture thereof is formed.
- compositions can be incorporated in the compositions.
- curing agents and curing catalysts of the kinds described in British Specifications Nos. 580,524 and 580,526, additional organic polyisocyanates, fillers, such as carbon. black, iron oxides, clay, asbestos, blanc fixe, whiting, lithopone, other inorganic or organic pigments other plasticizers such as tricresyl phosphate, dibutyl phthalate, butylphthalyl butyl glycollate, N-alky1-to1uenesulphonamides, stabilisers or anti-oxidants such as hydroquinone, N:N'- hexamethylene-bis-ortho-hydroxybenzamide, N- henyl-a-naphthylamine, N-phenyl-fi-naphthylamine and ma-bis-(Z hydroxy 3:5 dimethyl phenyl) -butane.
- compositions of the invention may be formed into films or other shapes or spread or calendered on to a substrate, for example, on to the surface of a fabric or on to the surface of a coated fabric.
- curing agents may be effected by heating, for example, in a mould which is preferably in a hydraulic press, or in hot air; periods of heating of from a few minutes to several hours at 100-150 C. are usual.
- organic solvents and/ or swelling agents may be used.
- compositions of the invention may be used in the fabrication of a variety of articles in which they may or may not be supported on a substrate and/or interspersed with a filler.
- they may be used for organic liquid-resistant articles of all kinds, for example, gaskets, packings, hose. diaphragms for pumps, as well as in the fabrication of flexible containers for fuels and the like. They may be used to provide the insulation for electrical conductors.
- They may also be used in the coating of balls f or'games, tyres and flexible materials generally, including fabrics, protective clothing, leather cloth and floor coverings. They may also be used in lacquers or varnishes, for finishing leather, paper, rubber, and plastic materials, and as components for paints.
- Intrinsic viscosity is defined as log; 1 C
- r is the viscosity of a dilute chloroform solution of the polymer divided by the viscosity of chloroform at the temperature of measurement
- C is the concentration expressed in grams per 100 cubic centimetres of solution.
- Example 1 2 parts of polyethylene sebacate modified with 3.85% of hexamethylene diisocyanate are added to 4 parts of polyvinyl chloride which is running on a rubber mill with the rolls maintained at a temperature of 125 C. The modified polyethylene sebacate is added in small amounts, and the mixing is continued until the mass is homogeneous.
- the modified polyethylene sebacate used in this example is obtained as follows:
- this low molecular weight polyester is heated in a vessel up to 75 C., 3.85 parts of hexamethylene diisocyanate are added and the mixture is stirred for 5 minutes. The mixture is then poured into metal trays, and the trays and contents are heated in an oven at C. for 4 hours.
- the hexamethylene diisocyanate modified polyethylene sebacate thus obtained is a hard tough material which is soluble in chloroform; it has an intrinsic viscosity of 0.73.
- Example 2 8 parts of polyvinyl chloride are run on a roller mill with rolls maintained at a temperature of 125 C. 2 parts of polyethylene sebacate modified with 7.35% of hexamethylene diisocyanate are added slowly to the polymer on the mill. Milling is continued until the mass is homogeneous.
- the modified polyethylene sebacate used in this example is obtained as follows:
- Example '3 V 1 part of the interpolymer of vinyl chloride and vinyl acetate in the proportion of 90: by weight is .nm :on .a .roller .mill with 1011s; maintained 'at agitemperature :of 1.00? jiIo this :polymer :is added 0.5.;partznf sthfi modified; polyethylene 'sebacate described in Example 2.. Mixing .is continued until the components are thoroughly blended.
- Example 4 l partof an interpo-lymer of. vinyl-ehloridezami vinyl acetate in about the proportion of 95:5 is run on a roller mill with the rolls maintainedat a temperatureofl C. 0.2,5part of the modified polyethylene .sebacate, c lescribed in Example 2 is' added slowly, and mixing is continued until the componentsare thoroughly blended. p
- Example 5 Two parts of polyvinyl chloride .are run on a roller mill withrolls maintained at 1'40"
- One part of polypropylene adipate modified with 4:5 of hexamethylene diisocyanate is added, slowly at firstjto 'thepolyvinyl chloride on :the mill.
- the rate or addition is increased after half of the modified polyester "hasbeen and, when the whole of the modified polyester has been added, milling is continued until the mass is homogeneous.
- This mix is sheeted out and pressed out'b'etwe'en stainless steel plates at a temperature of 170 C.
- the modified polypropylene adipatic used in this example is obtained as follows:
- Example '7 roll-er mill with .the temperature of the :rolls kept iste'ady at 140C.
- tMilling is continued tma'chieve homogeneity.
- the mix isrsheeted out andtpressed 30 between aluminium foil :sheets at *17 5C. A flexible, elear,. non-'brittle filmis obtained.
- ethylene adipate/sebaoatecopiolyq men used inthisexaniple isobtainedas follows 4'8? parts of adip'ie-acid, 673 parts .oissebaoi'c acid and 12 0 parts of ethylene glycol are heated together undercarbon dioxide :at 200" C. for 124 hours, after which time thedistillation ofwater has-ceased and the acldvalue ofthe ma'tei ial is about 1 milligram of KOH per-"gram. -Ethylene 40.
- glycol i'sfthen distilled-oh by heating at 200 Cat aipressure of. 0.1 mm.:o'f mercury for-Ahours;
- this ipolyester are mixed witn ss parts" of 'hexamethylene diisocyanate tor 5 mm utes at 80 C. The mixture is thentransferred to metal trays andheated in an oven' at' C.
- the hexamethylene diisocyanate modified polypropylene adipate thus obtained is a soft rubbery material; it has a molecular-weight greater than 10,000.
- Example 6 Two parts of polyvinyl chloride are. mixed with 1 part of, polypropylene sebacate modified with 3.36% of hexamethylene di'isocyanate'in the manner described in Example 5.
- the so obtained mix is .sheetedout. and pressed between. stainless steel plates at a temperature of 115C. for 2 minutes... 911 cooling under pressure.
- Asimilar film is.obtainedbyusing anflin g P91 ifi telil tide n in it acetate in chloroform. Itcontains adipi'cxacid and se- Y bacic. 'acid .in equal molecular proportions, and it" has a molecular weight greater'than IOJIOO;
- Example 8 I Ihe recipe, of Example .'7 is repeated. using an interpolymer of fvinylohloride and vinyl acetate 'in fthe ratio of 9515 place of the polyvinyl chloride. The film obtained is transparent, soft.
- I I ,A film obtained by. pressing the mix between stainless steel plates at C. is :soft,,flexi ble and transparent.
- the hexamethylene diisocyanate modified eth-. ylene adipate/sebacate copolymer thus obtained is a hard, tough, material which is insoluble in chloroform." It contains adipic acid and sebacic acid iii-the molecular proportions of '30: 70,-andit has a ⁇ molecular weight greater than 10,000; .lLfj E:vample1 f If Two' parts of polyvinyl chloride are run on a roller :mill with the rolls maintained at a temperature of 130 C: One part cfpolyhexamethylene glutarate modified with hexamethylene diisocyanate is added steadily; After addition is. completed,.
- Example 11 parts of polyvinyl chloride are mixed with if: part" of polyhexamethylene adipate' 'modified withhexamethylene diisocyanate in the manner described in Example 10.
- I I I I I I A flexible transparent film is obtained by pressing the mix at 175 C; between stainless steel plates.
- II I I I The modified p lyhexamethylene adipate' used in this example is obtained as follows:
- n of x s b gd s nai e .8. ?.I The mixture is then transferred -to metal trays 8 and-heated in an oven at C. for- 4*hours.
- the hexamethylene -diisocyanate 'modified polyhexamethyle'neglycol adipate thusobtained is a tough, hard, microcrystalline material'melt-" ing at 63 C.; it has a molecular weight greater than 10.000.
- the mixture is then transferred to metal trays and heated in an ovenat130 C. for 4 hours-
- the hexamethylene diisocyanate modified polyhexamethylene succinate thus obtained is a hard tough microcrystalline material; it has a -molecular weight greaterthan 10,000.
- the hexamethylene diisocyanate modified propylene adipate/laurate copolymer is a viscous liquid'havingan intrinsic viscosity in chloroform of v.0 13 I Example 14 9 24 hours.
- the product is a fairly viscous, brown liquid with an intrinsic viscosity of 0.06.
- the hexamethylene diisocyanate modified propylene adipate/stearate copolymer is a viscous liquid having an intrinsic viscosity of 0.18.
- Example 15 The recipe of Example 13 is repeated using in place of the modified propylene adipate/laurate copolymer a modified propylene adipate/ 12-hydroxystearate copolymer.
- the modified propylene adipate/12-hydroxystearate copolymer used in this example is obtained as follows:
- adipic acid 20 parts of lz-hydroxystearic acid (hydrogenated castor oil fatty acids) and 20.6 parts of propylene glycol are heated together under carbon dioxide at 200 C. for 1 hour, and then further heated at 200 C. at a pressure of 0.5 mm. of mercury for 6 hours.
- the product is a viscous brown liquid having an intrinsic viscosity of 0.06.
- the hexamethylene diisocyanate modified propylene adipate lz-hydroxystearate copolymer is a, viscous liquid having an intrinsic viscosity in chloroform of 0.27.
- a composition comprising from 20 to 100 parts by weight of a hydrocarbon polyisocyanatemodified polyester of a glycol and a dicarboxylic acid having a molecular weight greater than 10,000 and parts by weight of a vinyl chloride polymer selected from the group consisting of polyvinyl chloride and an interpolymer of a preponderating amount of vinyl chloride with another mono-olefinic compound copolymerizable therewith.
- a composition comprising from 20 to 100 parts by weight of a hydrocarbon polyisocyanatemodified polyester of a glycol, a monocarboxylic acid, and a dicarboxylic acid having a molecular Weight greater than 10,000 and 100 parts by Weight of a vinyl chloride polymer selected from the group consisting of polyvinyl chloride and an interpolymer of a preponderating amount or vinyl chloride with another mono-olefinic compound copolymerizable therewith.
Description
Patented Aug. 5, 1952 COMPOSITIONS COMPRISING POLYISO-' CYANATE MODIFIED POLYESTERS AND VINYL CHLORIDE POLYMERS David Hay Cofiey, Owen BurchellEdgar, Thomas James Meyrick, andJohn Thomas Watts, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain -No Drawing. Application January 24, 1949, Se-
rial No. 72,552. In Great Britain January 30,
This invention relates to compositions co-mprising polymeric materials, more particularly to compositions comprising organic polyisocyanate modified polyesters in admixture with polyvinyl chloride, and to articles and other compositions made therefrom.
According to the present invention we provide compositions comprising organic polyisocyanate modified polyester in uniform admixture with polyvinyl chloride.
We have found that in such compositions the polyisocyanate modified polyester has the properties of an excellent plasticizer and is of particular advantage because it does not readily volatilise or migrate from the compositions. The polyisocyanate modified polyesters show considerable advantage over the unmodified polyesters in that they are much more readily mixed into the polyvinvyl chloride, and in that any tendency to separate from or bleed out of the compositions i either very much less or completely absent.
Compositions wherein the organic polyisocyanate modified polyester has an excellent plasticising efiect on the polyvinyl chloride are those wherein from 20 to 100 parts by weight of modified polyester are used per 100 parts of polyvinyl chloride.
The polyvinyl chloride may housed in the form of an interpolymer of vinyl chloride with one or more other compounds of polymerisable olefinic nature which is or are not used in preponderate ing amount, for example, other vinyl esters such as vinyl acetate, unsymmetrical dichloroethylene, styrene, and the esters, nitriles and amides of acrylic; methacrylic, f'umaric and maleic acids.
The polyester may be formed conveniently by heating the selected reactants at polymerizing temperatures in the absence of air or oxygen under conditions whereby water is removed from the reaction. mixture in any conventional manner. Usually, the polyester is formed from a glycol and a dibasic carboxylic acid or an esterforming derivative of either or both of these or a mixture of two ore more of such components. If desired, a proportion of a monobasic car-'- boxylic acid or an ester-forming derivative thereof be included among the reactants.
Examples of glycol-s are ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1:12-octadecanediol and pentaglycol.
Examples of dibasic carboxylic acids are malonic, succinic, glutaric, adipic, p-xnethyl- 2 Claims. (Cl.260--22) adipic, pimelic, suberic, azelaic, sebacic, undeca-nedioic, brassylic, isophthalic, hexahydroterephthali'c, p-phenylene-diaceticand acetonedicarboxylic acid;
' Especially suitable monobasic carboxylic acids.
are those containing from 10 to 18 carbon atoms, for example, laurio, myristic, palmitic and stearic acids, as well as hydroxy-derivatives of these, for example, hydroxy-stearic acid. Usually, the polyesters used have a molecular weight of 1000 or more. Molecular weight is usually determined by analysing the end groups of the polyesters, and by calculation from the results thereof.
The polyesters are modified with the organic polyisocyanate in known manner, for example, by mixing them by stirring, milling or kneading, with the organic polyisocyanate and then heating the mixture, for example, at a temperature of mil-200 C. for a period of 10. to 720 minutes. Up to 15%, usually at least 3% by weight of the pclyisocyanate is used. A factor which influences the choice of the quantity of: the organic polyisocyanate-is the molecular weight of the final product, i. e. the organic polyisocyanate modified polyester. Usually, the molecular weight of the organic polyisocyanate modified polyester isgreater than10,00(), and a sufficiency of the polyisocyanate is used to allow the formation of a final product of this molecular weight. An indi cation of the molecular weight'may be obtained by measurement of intrinsic viscosity, and those modified polyesters having intrinsic viscosities in chloroform of 0.6 or more may be taken as conforming to the molecular weight requirement mentioned above. Further, useful compositions have been obtained from organic polyisocyanate modified polyesters which are not soluble in .501- vents such as chloroform, and viscosity measurements have not been made on these. Since these modified polyesters have been made with the use of relatively large proportions of'the polyisocyanates, their molecular weights may be'taken as well above the requirement mentioned. When the polyester contains a proportion of a monocarboxylic acid, the molecular weight may be below the requirement mentioned.
Examples of organic polyisocyanates areh drocarbon polyisocyanates including ethylene diisocyanate, trimethylene diisocyanate, tetramethylen diisocyanate, ,hexamethylene diisocyanate, decamethylene diisocyanate, p-phenylenediisccyanate, m-phenylene diisocyanate,
naphthalene diisocyanates, benzene l:3:5-tri-.
isocyanate, toluene-2 14:6-triisocyanate, ethylbenzcne 2 :4:6 triisocyanate, monochlo-roben- The organic polyisocyanate modified polyester or a mixture of more than one such modified polyester may be brought into uniform admixture with the polyvinyl chloride in a number of ways.
For instance, the components may be mixed or milled together, if desired, at a moderately elevated temperature, as such or in the presence of organic liquids, for example, nitroparafiins, chloroform, ethylene dichloride, benzene I and mixtures of ethyl acetate with ethylene dichloride which are solvents or swelling agents for one or both of the components; the organic liquids may be removed as and when convenient. Alternatively, solutions of the components may be mixed.
If desired, the organic polyisocyanate modified polyester may be formed in situ, as by incorporating the polyester or mixture of polyesters with the polyvinyl chloride and by also incorporating with such mixture an organic polyisccyanate or mixture of organic polyisocyanates, and thereafter subjecting the composition to a heating operation whereby the modified polyester or mixture thereof is formed.
Other ingredients can be incorporated in the compositions. These include curing agents and curing catalysts of the kinds described in British Specifications Nos. 580,524 and 580,526, additional organic polyisocyanates, fillers, such as carbon. black, iron oxides, clay, asbestos, blanc fixe, whiting, lithopone, other inorganic or organic pigments other plasticizers such as tricresyl phosphate, dibutyl phthalate, butylphthalyl butyl glycollate, N-alky1-to1uenesulphonamides, stabilisers or anti-oxidants such as hydroquinone, N:N'- hexamethylene-bis-ortho-hydroxybenzamide, N- henyl-a-naphthylamine, N-phenyl-fi-naphthylamine and ma-bis-(Z hydroxy 3:5 dimethyl phenyl) -butane.
The compositions of the invention may be formed into films or other shapes or spread or calendered on to a substrate, for example, on to the surface of a fabric or on to the surface of a coated fabric. If curing agents are used, curing may be effected by heating, for example, in a mould which is preferably in a hydraulic press, or in hot air; periods of heating of from a few minutes to several hours at 100-150 C. are usual. If desired, to facilitate shaping or spreading, organic solvents and/ or swelling agents may be used.
The compositions of the invention may be used in the fabrication of a variety of articles in which they may or may not be supported on a substrate and/or interspersed with a filler. For instance, they may be used for organic liquid-resistant articles of all kinds, for example, gaskets, packings, hose. diaphragms for pumps, as well as in the fabrication of flexible containers for fuels and the like. They may be used to provide the insulation for electrical conductors.
They may also be used in the coating of balls f or'games, tyres and flexible materials generally, including fabrics, protective clothing, leather cloth and floor coverings. They may also be used in lacquers or varnishes, for finishing leather, paper, rubber, and plastic materials, and as components for paints.
Intrinsic viscosity, as used herein, is defined as log; 1 C
where r is the viscosity of a dilute chloroform solution of the polymer divided by the viscosity of chloroform at the temperature of measurement,
and C is the concentration expressed in grams per 100 cubic centimetres of solution.
The invention is. illustrated but not limited by I the following examples in which parts and percentages are expressed by weight.
Example 1 2 parts of polyethylene sebacate modified with 3.85% of hexamethylene diisocyanate are added to 4 parts of polyvinyl chloride which is running on a rubber mill with the rolls maintained at a temperature of 125 C. The modified polyethylene sebacate is added in small amounts, and the mixing is continued until the mass is homogeneous.
The resulting mix is pressed for two minutes at 141 C. between stainless steel plates, and is cooled under pressure. A transparent, flexible sheet is obtained,
The modified polyethylene sebacate used in this example is obtained as follows:
71.3 parts of ethylene glycol and 202 parts of sebacic acid are heated together under carbon dioxide at 210-220 C. for 28 hours. The product is a fawn-coloured, brittle wax melting at C. and having a molecular weight of 3,500.
parts of this low molecular weight polyester are heated in a vessel up to 75 C., 3.85 parts of hexamethylene diisocyanate are added and the mixture is stirred for 5 minutes. The mixture is then poured into metal trays, and the trays and contents are heated in an oven at C. for 4 hours. The hexamethylene diisocyanate modified polyethylene sebacate thus obtained is a hard tough material which is soluble in chloroform; it has an intrinsic viscosity of 0.73.
Example 2 8 parts of polyvinyl chloride are run on a roller mill with rolls maintained at a temperature of 125 C. 2 parts of polyethylene sebacate modified with 7.35% of hexamethylene diisocyanate are added slowly to the polymer on the mill. Milling is continued until the mass is homogeneous.
The so obtained mix is sheeted out and pressed between stainless steel plates at a temperature of 141C. for two minutes. After cooling under pressure, a transparent, flexible sheet is obtained. Similar results are obtained by using twice the quantity of the modified polyethylene sebacate, but a more flexible film is obtained.
The modified polyethylene sebacate used in this example is obtained as follows:
808 parts of sebacic acid and 620 parts of ethylene glycol are heated together under nitrogen at 200220 C. for 12 hours, after which time the distillation of water has ceased and the acid value of the material is less than 1 milligram of KOH per gram. Ethylene glycol is then distilled off by heating at 220C. at a pressure of 15 mm. of mercury for 5 hours. The product is a white, brittle wax, melting at 70 C.; it has a molecular weight of 2,500.
.100 parts of this polyester are heated to 85 C., 7.35 parts of hexamethylene diisocyanate are added, and the mixture is stirred for 15 minutes at 85-90 C. The mixture is then transferred to metal trays and heated in an oven at C. for 2 hours.
'flfheihexamethylene diisocyanate modified polyethrlene-sebacate :thus obtained :is a :hard tough material. which iSlSQlU-blfi in chloroiorm; .11; L has anlintrinsicviscosity-of 1.11
Example '3 V 1 part of the interpolymer of vinyl chloride and vinyl acetate in the proportion of 90: by weight is .nm :on .a .roller .mill with 1011s; maintained 'at agitemperature :of 1.00? jiIo this :polymer :is added 0.5.;partznf sthfi modified; polyethylene 'sebacate described in Example 2.. Mixing .is continued until the components are thoroughly blended.
The :resulting .mix ;shee t.ed off the .mill and Dressedbetweenstainless steel plates for two minutes .at .1125. vC. .jA. acolourless, transparent ;:and flexiblafilmisphtained.
' Example 4 l partof an interpo-lymer of. vinyl-ehloridezami vinyl acetate in about the proportion of 95:5 is run on a roller mill with the rolls maintainedat a temperatureofl C. 0.2,5part of the modified polyethylene .sebacate, c lescribed in Example 2 is' added slowly, and mixing is continued until the componentsare thoroughly blended. p
, The so obtained-mix is. sheeted Qfi the, mill, -a.nd the rough sheet is pressed between stainless steel plates for two minutes at 141 C. A flexible, transparent film is obtained.
Example 5 Two parts of polyvinyl chloride .are run on a roller mill withrolls maintained at 1'40" One part of polypropylene adipate modified with 4:5 of hexamethylene diisocyanate is added, slowly at firstjto 'thepolyvinyl chloride on :the mill. The rate or addition is increased after half of the modified polyester "hasbeen and, when the whole of the modified polyester has been added, milling is continued until the mass is homogeneous.
This mix is sheeted out and pressed out'b'etwe'en stainless steel plates at a temperature of 170 C.
for 2 minutes. After cooling under pressure, a transparent flexible sheet is obtained.
The modified polypropylene adipatic used in this example is obtained as follows:
584 parts of adipic acid and 8 parts of pro pylenev glycol are heated together under nitrogen at "200 C. for 1'0 hours, .ajfter which time the distillation ofv water has ceased and the'acid value, o f the material ,isless than .1 milligram of KOCH per gram. Propylene glycol is. then distilled off by heating at 200 C. at. a pressure. 0105. cc. .of mercury for '6 hours. The product is alye'llow viscous liquid; ithasajmoleoular weighto'f ,2,8 U,0. 100 parts of "this polyester are. heated up to C., 4.5 parts'ofhexamethylene diisocyanate areladded, and the mixture is stirred for .10 mina:soft,ifiexible, homogeneous, transparentfilmefs obtained." V .The modified :polypropylene sebaoate'; used '1' in -thisaexample isobtainedxasiollowsfi 404 parts of sebacic acid and 167 parts :of; propylene. glycol; areheated together: under; nitrogen-sat. 200 50. for .24 :lroursrafter-which time st'he distillation 'ofzwater-hadmease'd. Propylenerglycoliis-then distilled off byJheating at 200 Qzatia pressure; of 05mm. .of mercury for T6 hours. The
product isia dark brown viscous liquid.
1061331135 of this polyester are mixed with-3.36
parts -.of hexamethylene :diiso'cyanate :atx C.
"The mixture is then transferred.:to .metalitrays and.heate.d::at 140--l50.C.-for 2 hours. i
'Thehexamethylene.dlisooyanatemodifiedpolypropylene L-sebacate thusobtained is a darkbrown rubbery material; it has a .molecular weight greater than 10,000. v
Example '7 roll-er ;mill with .the temperature of the :rolls kept iste'ady at 140C. One :part Qf-"anethyIene-adi-F pate/sebacate copolymer modified with hexamethylene diisocyanate added at such a speed as :to allow the. mill to continue irunnin'g withno heatiinthe band. tMilling is continued tma'chieve homogeneity. The mix isrsheeted out andtpressed 30 between aluminium foil :sheets at *17 5C. A flexible, elear,. non-'brittle filmis obtained.
. ifI'he-modified ethylene adipate/sebaoatecopiolyq men used inthisexaniple isobtainedas follows 4'8? parts of adip'ie-acid, 673 parts .oissebaoi'c acid and 12 0 parts of ethylene glycol are heated together undercarbon dioxide :at 200" C. for 124 hours, after which time thedistillation ofwater has-ceased and the acldvalue ofthe ma'tei ial is about 1 milligram of KOH per-"gram. -Ethylene 40.
glycol i'sfthen distilled-oh by heating at 200 Cat aipressure of. 0.1 mm.:o'f mercury for-Ahours; The
product is-a white .waximelting at 48 0.; it :ha's'a. molecular weightsofSTOO. i i
parts of this ipolyester are mixed witn ss parts" of 'hexamethylene diisocyanate tor 5 mm utes at 80 C. The mixture is thentransferred to metal trays andheated in an oven' at' C.
ior lhours- 'fIhe hexameth-ylene diisocyan'ate modified ethylene adipate/sebacate copolymer thus fobtaine-disa hard tough-material whichiis tinso'luble utes. The mixture is then .transierred to metal.
trays and heated in an oven at 130 C. for'5 hours.
The hexamethylene diisocyanate modified polypropylene adipate thus obtained is a soft rubbery material; it has a molecular-weight greater than 10,000.
. Example 6 Two parts of polyvinyl chloride are. mixed with 1 part of, polypropylene sebacate modified with 3.36% of hexamethylene di'isocyanate'in the manner described in Example 5.
The so obtained mix is .sheetedout. and pressed between. stainless steel plates at a temperature of 115C. for 2 minutes... 911 cooling under pressure.
Asimilar film is.obtainedbyusing anflin g P91 ifi telil tide n in it acetate in chloroform. Itcontains adipi'cxacid and se- Y bacic. 'acid .in equal molecular proportions, and it" has a molecular weight greater'than IOJIOO;
Example 8 I Ihe recipe, of Example .'7 is repeated. using an interpolymer of fvinylohloride and vinyl acetate 'in fthe ratio of 9515 place of the polyvinyl chloride. The film obtained is transparent, soft.
and flexible. l
' I 1 Example ,9
Two parts of polyvinyl chloridearerun -on a roller mill with, the temperatureflkept constant. at 135." C. One part of an ethylene adipatefseb acate vcopoly'mer modified with,3.8 .hexamethy1;
one diisocyan'ate is added steadily.- After com- ;plete addition milling is continuedtie-give homo-p geneity, I I ,A, film obtained by. pressing the mix between stainless steel plates at C. is :soft,,flexi ble and transparent. V
thearatio. of 95:5 .in place of ther'tpolyvinyl chloride. 3.
' The modified ethylene" adipate/sebacate; i'copolymer used inthiseexample is obtainedea's fOllOWSZ'. .1.. :1 1 i 292; parts of. adipic acid, 943parts of sebacic acid and 1240 parts ofethylene glycol are heated together-under carbon-dioxide .at 200C. for 20 hours, after which .time the acid value of the material is below 1 milligram of KOH pergram. Ethylene glycolis thendistilledtoff by heating at 200 C. at .apressure' of 1 mmyofmercury for 5 hours. The product is a whitecrystalline wax meltingat59C. i 1
100 parts of this polyesterare mixed'with 3.8% hexamethylene diisocyanate at 80 C.- The mixture is. then transferred to metal trays" and heated at 130 C. for4hours.
The hexamethylene diisocyanate modified eth-. ylene adipate/sebacate copolymer thus obtained is a hard, tough, material which is insoluble in chloroform." It contains adipic acid and sebacic acid iii-the molecular proportions of '30: 70,-andit has a} molecular weight greater than 10,000; .lLfj E:vample1 f If Two' parts of polyvinyl chloride are run on a roller :mill with the rolls maintained at a temperature of 130 C: One part cfpolyhexamethylene glutarate modified with hexamethylene diisocyanate is added steadily; After addition is. completed,. milling is further continued to'yie'ld a homogeneous product. The material is sheeted out and pressed between aluminum foil with a platten temperature of"17-5 C. The film-so obtained is soft, flexible and transparent,-a nd it hasa good tearresistance.-
Themodified polyhexamethylene .glutarate used in lthisexample is .obtained as follows-:-
1792 parts ,of glutaric acid'and 7210 parts of hexamethylene glycol'are heated together under nitrogen at 200 C. for 2 hours, and then further heated at 200 C. at a pressure-of 0.2 mm. of mercury for 4 hours. The'product is a. white brittle wax, melting at 27 Ci; it hasa molecular weight of 3200.
100 parts of this polyester'are mixed with5.-3. parts of hexamethylene diisocyanate at 70 Cl The mixture is then transferred to metal trays and heated in anoven at 130 C. for 4 hours. r The hexamethylene. diisocyanate -m'o'difiedpolyhexamethyl'ene glutarate thus obtained is a soft rubbery material; it has a molecular weight oi'greaterthan-IQOOO. r 1
Example 11 parts of polyvinyl chloride are mixed with if: part" of polyhexamethylene adipate' 'modified withhexamethylene diisocyanate in the manner described in Example 10. I I I I A flexible transparent film is obtained by pressing the mix at 175 C; between stainless steel plates. II I I The modified p lyhexamethylene adipate' used in this example is obtained as follows:
330 parts of adipic acid and Z'IQ parts of hexamethylene glycol are heated together under 'n i tro 'gn 'at 200 C. for 3 hours; and then further heated at 200 Cf'at a pressure of 1.0 mm; of mercury for 2 hours. The product, is awhite, brittlewax'melting at 63 C'.; it has a molecular weight of 2,800.- 100 parts of this polyester are'mixed'with 7,67
n of x s b gd s nai e .8. ?.I The mixture is then transferred -to metal trays 8 and-heated in an oven at C. for- 4*hours. The hexamethylene -diisocyanate 'modified polyhexamethyle'neglycol adipate thusobtained is a tough, hard, microcrystalline material'melt-" ing at 63 C.; it has a molecular weight greater than 10.000.
Eieample 12 The recipe of- Example 11 is repeated usingin place of the modified polyhexamethyleneadipate a polyhexamethylene succinate modified with-.-
parts "of hexamethylene diisocyanate at809 C.
The mixtureis then transferred to metal trays and heated in an ovenat130 C. for 4 hours- The hexamethylene diisocyanate modified polyhexamethylene succinate thus obtained is a hard tough microcrystalline material; it has a -molecular weight greaterthan 10,000.
Exam le 13 2 parts of polyvinyl chloride are run on a roller mill. with rolls maintained steady at C. One part of a propylene adipate/laurate copolymer modified with hexamethylene diisocyanate is'added steadilyfto the polyvinyl chloride on the mill. The' materials are easily compatible, but a further'S minutes milling is given after coinpl e'tion of additions, in order, to ensure homog'eneity., l I
The mix issheeted out] and pressed between stainless steel plates with the press temperature 1 at C. A soft, flexible'film which does' not show opacity on stretching and which'has good tear strength is obtained. I I I I The modified propylene. adipate/laurate copolymer used in this example is obtained as follows:, Y I
73 parts of adipicacid. 66.6 parts of lauric acid and 55.1 parts of propylene glycol are heated together under carbon dioxide. at 200-220 C. for 1 8ho urs The product is a fairly viscous, brown liquid'withan'intrinsic viscosity of 0.06. 100'p'arts'of this polyester are mixed with} parts'of hexamethylene diisocyanate at-70." C, The mix ture is then transferred to metal trays and heated'in an oven at 130C. for 4 hours.
The hexamethylene diisocyanate modified propylene adipate/laurate copolymer is a viscous liquid'havingan intrinsic viscosity in chloroform of v.0 13 I Example 14 9 24 hours. The product is a fairly viscous, brown liquid with an intrinsic viscosity of 0.06.
100 parts of this polyester are mixed with 7 parts of hexamethylene diisocyanate at 70 C. The mixture is then transferred to metal trays and heated in an oven at 130 C. for 4 hours.
The hexamethylene diisocyanate modified propylene adipate/stearate copolymer is a viscous liquid having an intrinsic viscosity of 0.18.
Example 15 The recipe of Example 13 is repeated using in place of the modified propylene adipate/laurate copolymer a modified propylene adipate/ 12-hydroxystearate copolymer.
A good, clear film of good flexibility and tear,
resistance is obtained.
The modified propylene adipate/12-hydroxystearate copolymer used in this example is obtained as follows:
30 parts of adipic acid, 20 parts of lz-hydroxystearic acid (hydrogenated castor oil fatty acids) and 20.6 parts of propylene glycol are heated together under carbon dioxide at 200 C. for 1 hour, and then further heated at 200 C. at a pressure of 0.5 mm. of mercury for 6 hours. The product is a viscous brown liquid having an intrinsic viscosity of 0.06.
100 parts of this polyester are mixed with 20 parts of hexamethylene diisocyanate at 70 C. The mixture is then transferred to metal trays and heated in an oven at 130 C. for 4 hours.
The hexamethylene diisocyanate modified propylene adipate lz-hydroxystearate copolymer is a, viscous liquid having an intrinsic viscosity in chloroform of 0.27.
We claim:
1. A composition comprising from 20 to 100 parts by weight of a hydrocarbon polyisocyanatemodified polyester of a glycol and a dicarboxylic acid having a molecular weight greater than 10,000 and parts by weight of a vinyl chloride polymer selected from the group consisting of polyvinyl chloride and an interpolymer of a preponderating amount of vinyl chloride with another mono-olefinic compound copolymerizable therewith.
2. A composition comprising from 20 to 100 parts by weight of a hydrocarbon polyisocyanatemodified polyester of a glycol, a monocarboxylic acid, and a dicarboxylic acid having a molecular Weight greater than 10,000 and 100 parts by Weight of a vinyl chloride polymer selected from the group consisting of polyvinyl chloride and an interpolymer of a preponderating amount or vinyl chloride with another mono-olefinic compound copolymerizable therewith.
DAVID HAY COFFEY. OWEN BURCHELL EDGAR. THOMAS JAMES MEYRICK. JOHN THOMAS WATTS.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,036,009 Wright ..4. Mar. 31, 1936 2,282,827 Rothrock May 12, 1942 2,422,271 Vaala et al. June 17, 1947 FOREIGN PATENTS Number Country Date 586,826 Great Britain Apr. 1, 1947
Claims (1)
1. A COMPOSITION COMPRISING FROM 20 TO 100 PARTS BY WEIGHT OF A HYDROCARBON POLYISOCYANATEMODIFIED POLYESTER OF A GLYCOL AND A DICARBOXYLIC ACID HAVING A MOLECULAR WEIGHT GREATER THAN 10,000 AND 100 PARTS BY WEIGHT OF A VINYL CHLORIDE POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYVINYL CHLORIDE AND AN INTERPOLYMER OF A PREPONDERATING AMOUNT OF VINYL CHLORIDE WITH ANOTHER MONO-OLEFINIC COMPOUND COPOLYMERIZABLE THEREWITH.
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US72552A Expired - Lifetime US2606162A (en) | 1948-01-30 | 1949-01-24 | Compositions comprising polyisocyanate modified polyesters and vinyl chloride polymers |
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US2725366A (en) * | 1952-09-29 | 1955-11-29 | Goodyear Tire & Rubber | Storable isocyanate-modified polyesters |
US2726225A (en) * | 1954-04-14 | 1955-12-06 | Cambridge Ind Company | Polyvinyl acetate plasticized with a polyester |
DE953917C (en) * | 1953-08-07 | 1956-12-06 | Chemieprodukte G M B H | Process for the production of rubber-elastic, fuel-resistant sealing compounds |
US2814604A (en) * | 1955-02-07 | 1957-11-26 | Goodrich Co B F | Compositions comprising diisocyanatelinked elastomers and silicon dioxide |
US2838428A (en) * | 1949-05-28 | 1958-06-10 | Gen Electric | Plasticized vinyl halide resins and electrical conductors insulated therewith |
US2851436A (en) * | 1955-09-26 | 1958-09-09 | Armstrong Cork Co | Method of making dhsocyanate-modified polyester with polymerized vinyl halide |
US2872430A (en) * | 1956-07-31 | 1959-02-03 | Armstrong Cork Co | Composition comprising a diisocyanate modified polyester and polymerized vinyl chloride |
US2888433A (en) * | 1955-09-26 | 1959-05-26 | Armstrong Cork Co | Binder of dhsocyanate modified unsaturated polyester and vinyl chloride polymer and method of preparing same |
US2891876A (en) * | 1956-10-10 | 1959-06-23 | Union Carbide Corp | Primers for vinyl chloride resin coatings |
US2893969A (en) * | 1956-01-13 | 1959-07-07 | Armstrong Cork Co | Composition containing diisocyanatemodified polyester, polymerized vinyl halide, filler and aromatic diisocyanate |
US2898312A (en) * | 1954-10-06 | 1959-08-04 | Philip H Rhodes | Production of a cellular polyvinyl polyester plastic composition |
US2929737A (en) * | 1953-08-13 | 1960-03-22 | Bayer Ag | Coated textiles and method of producing the same |
US2935487A (en) * | 1956-05-31 | 1960-05-03 | Gen Electric | Polyester-polyisocyanate insulating materials |
US2943072A (en) * | 1955-03-15 | 1960-06-28 | Armstrong Cork Co | Method of controlling the gelation of filled diisocyanate modified polyester |
US2956903A (en) * | 1957-12-23 | 1960-10-18 | Ici Australia Ltd | Composition and method for coating polyester or polyamide fabrics, and fabrics coated thereby |
US2979423A (en) * | 1957-09-25 | 1961-04-11 | Johnson & Johnson | Isocyanate modified vinyl chloride copolymer film backed adhesive tape |
US2981637A (en) * | 1957-04-02 | 1961-04-25 | Spencer David Patrick | Coating of fabrics |
US3024216A (en) * | 1958-07-28 | 1962-03-06 | Union Carbide Corp | Compositions of partially hydrolyzed vinyl chloride-vinyl acetate copolymers and polyurethane resins, polyethylene coated with same and process for making coated article |
US3069287A (en) * | 1961-02-16 | 1962-12-18 | Mobay Chemical Corp | Coating polycarbonate plastics |
US3144352A (en) * | 1962-10-15 | 1964-08-11 | Ampex | Magnetic tape having a binder mixture of polyurethane resin and a copolymer of vinylidene chloride and acrylonitrile |
US3149995A (en) * | 1961-04-28 | 1964-09-22 | Rca Corp | Magnetic recording element and method of preparation thereof |
US3204013A (en) * | 1961-05-23 | 1965-08-31 | Dayco Corp | Light stabilized compositions comprising polyvinyl chloride, polyurethane and ethylene oxide |
US3210439A (en) * | 1959-11-02 | 1965-10-05 | Ici Ltd | Coating and adhesive compositions comprising vinyl chloride polymers and polyisocyanate modified polyesters of aliphatic acids and diols with carbon:oxygen content of at least 5:2 |
US3210215A (en) * | 1959-11-02 | 1965-10-05 | Ici Ltd | Process for coating substrates with compositions comprising vinyl chloride polymers and polyisocyanate modified polyesters of aliphatic acids and diols with carbon: oxygen content of at least 5:2 |
US3216846A (en) * | 1963-01-21 | 1965-11-09 | Gevaert Photo Prod Nv | Process for producing a magnetic recording material |
US3242005A (en) * | 1961-02-25 | 1966-03-22 | Sony Corp | High density magnetic recording medium |
US3257261A (en) * | 1957-05-15 | 1966-06-21 | Du Pont | Composition comprising a blend of a vinyl chloride polymer and a polyurethane |
US3283031A (en) * | 1958-02-13 | 1966-11-01 | Gen Tire & Rubber Co | Rigid polyvinyl chloride compositions containing polyurethane elastomers, and a copolymer of a styrene and an ethylenically unsaturated nitrile |
US3395109A (en) * | 1962-10-08 | 1968-07-30 | Spalding A G & Bros Inc | Golf ball cover composition comprising a blend of polyesterurethane elastomers |
US3423346A (en) * | 1965-10-19 | 1969-01-21 | Ppg Industries Inc | Latex coating compositions |
US3440086A (en) * | 1964-12-23 | 1969-04-22 | Firestone Tire & Rubber Co | Polyurethane precursor-viscosity builder and curing agent coating composition and method of coating therewith |
US3549407A (en) * | 1968-02-29 | 1970-12-22 | Du Pont | Process for applying a textured decorative coating to a metal substrate and article thereof |
JPS5014664B1 (en) * | 1970-05-12 | 1975-05-29 | ||
US3914480A (en) * | 1962-12-07 | 1975-10-21 | John L Lang | Process for the preparation of a fly fishing line and the resulting article |
US3984492A (en) * | 1973-08-29 | 1976-10-05 | Fuji Photo Film Co., Ltd. | Coating composition for polyester resin |
US4049611A (en) * | 1975-11-19 | 1977-09-20 | Monsanto Company | Modified polyester polyblends and preparation thereof |
US4049747A (en) * | 1971-01-21 | 1977-09-20 | Stauffer Chemical Company | Crosslinked vinyl halide polymers as flame retardant additives for thermoplastics |
US4089911A (en) * | 1976-04-30 | 1978-05-16 | Kao Soap Co., Ltd. | Process for improving the thermal stability of polyurethane-containing resin composition |
US4256852A (en) * | 1978-02-10 | 1981-03-17 | Victor Company Of Japan, Ltd. | Binder composition for magnetic recording tape |
US4350792A (en) * | 1979-03-01 | 1982-09-21 | Stauffer Chemical Company | Blend of internally plasticized vinyl chloride copolymer and polyurethane elastomer |
EP0172993A1 (en) * | 1984-07-30 | 1986-03-05 | DeSOTO, INC. | Low temperature-curing polyester urethane systems |
US4594366A (en) * | 1983-06-29 | 1986-06-10 | Union Carbide Corporation | Connected branched polyols and polyurethanes based thereon |
US4804768A (en) * | 1986-09-30 | 1989-02-14 | Union Carbide Corporation | Process for producing epoxyorganoalkoxysilanes |
US4923735A (en) * | 1987-12-31 | 1990-05-08 | Stamicarbon B.V. | Moulded printed circuit board |
EP0409586A2 (en) * | 1989-07-18 | 1991-01-23 | Tosoh Corporation | Vinyl chloride resin-based composition and packings made therefrom |
US5929153A (en) * | 1994-12-15 | 1999-07-27 | Tosoh Corporation | Vinyl chloride-based polymer-polyurethane composite and method of producing the same |
EP0934983A1 (en) * | 1998-02-04 | 1999-08-11 | Magna Investments N.V. | Polymer compositions |
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Cited By (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2838428A (en) * | 1949-05-28 | 1958-06-10 | Gen Electric | Plasticized vinyl halide resins and electrical conductors insulated therewith |
US2725366A (en) * | 1952-09-29 | 1955-11-29 | Goodyear Tire & Rubber | Storable isocyanate-modified polyesters |
DE953917C (en) * | 1953-08-07 | 1956-12-06 | Chemieprodukte G M B H | Process for the production of rubber-elastic, fuel-resistant sealing compounds |
US2929737A (en) * | 1953-08-13 | 1960-03-22 | Bayer Ag | Coated textiles and method of producing the same |
US2726225A (en) * | 1954-04-14 | 1955-12-06 | Cambridge Ind Company | Polyvinyl acetate plasticized with a polyester |
US2898312A (en) * | 1954-10-06 | 1959-08-04 | Philip H Rhodes | Production of a cellular polyvinyl polyester plastic composition |
US2814604A (en) * | 1955-02-07 | 1957-11-26 | Goodrich Co B F | Compositions comprising diisocyanatelinked elastomers and silicon dioxide |
US2943072A (en) * | 1955-03-15 | 1960-06-28 | Armstrong Cork Co | Method of controlling the gelation of filled diisocyanate modified polyester |
US2851436A (en) * | 1955-09-26 | 1958-09-09 | Armstrong Cork Co | Method of making dhsocyanate-modified polyester with polymerized vinyl halide |
US2888433A (en) * | 1955-09-26 | 1959-05-26 | Armstrong Cork Co | Binder of dhsocyanate modified unsaturated polyester and vinyl chloride polymer and method of preparing same |
US2893969A (en) * | 1956-01-13 | 1959-07-07 | Armstrong Cork Co | Composition containing diisocyanatemodified polyester, polymerized vinyl halide, filler and aromatic diisocyanate |
US2935487A (en) * | 1956-05-31 | 1960-05-03 | Gen Electric | Polyester-polyisocyanate insulating materials |
US2872430A (en) * | 1956-07-31 | 1959-02-03 | Armstrong Cork Co | Composition comprising a diisocyanate modified polyester and polymerized vinyl chloride |
US2891876A (en) * | 1956-10-10 | 1959-06-23 | Union Carbide Corp | Primers for vinyl chloride resin coatings |
US2981637A (en) * | 1957-04-02 | 1961-04-25 | Spencer David Patrick | Coating of fabrics |
US3257261A (en) * | 1957-05-15 | 1966-06-21 | Du Pont | Composition comprising a blend of a vinyl chloride polymer and a polyurethane |
US2979423A (en) * | 1957-09-25 | 1961-04-11 | Johnson & Johnson | Isocyanate modified vinyl chloride copolymer film backed adhesive tape |
US2956903A (en) * | 1957-12-23 | 1960-10-18 | Ici Australia Ltd | Composition and method for coating polyester or polyamide fabrics, and fabrics coated thereby |
US3283031A (en) * | 1958-02-13 | 1966-11-01 | Gen Tire & Rubber Co | Rigid polyvinyl chloride compositions containing polyurethane elastomers, and a copolymer of a styrene and an ethylenically unsaturated nitrile |
US3024216A (en) * | 1958-07-28 | 1962-03-06 | Union Carbide Corp | Compositions of partially hydrolyzed vinyl chloride-vinyl acetate copolymers and polyurethane resins, polyethylene coated with same and process for making coated article |
US3210439A (en) * | 1959-11-02 | 1965-10-05 | Ici Ltd | Coating and adhesive compositions comprising vinyl chloride polymers and polyisocyanate modified polyesters of aliphatic acids and diols with carbon:oxygen content of at least 5:2 |
US3210215A (en) * | 1959-11-02 | 1965-10-05 | Ici Ltd | Process for coating substrates with compositions comprising vinyl chloride polymers and polyisocyanate modified polyesters of aliphatic acids and diols with carbon: oxygen content of at least 5:2 |
US3069287A (en) * | 1961-02-16 | 1962-12-18 | Mobay Chemical Corp | Coating polycarbonate plastics |
US3242005A (en) * | 1961-02-25 | 1966-03-22 | Sony Corp | High density magnetic recording medium |
US3149995A (en) * | 1961-04-28 | 1964-09-22 | Rca Corp | Magnetic recording element and method of preparation thereof |
US3204013A (en) * | 1961-05-23 | 1965-08-31 | Dayco Corp | Light stabilized compositions comprising polyvinyl chloride, polyurethane and ethylene oxide |
US3395109A (en) * | 1962-10-08 | 1968-07-30 | Spalding A G & Bros Inc | Golf ball cover composition comprising a blend of polyesterurethane elastomers |
US3144352A (en) * | 1962-10-15 | 1964-08-11 | Ampex | Magnetic tape having a binder mixture of polyurethane resin and a copolymer of vinylidene chloride and acrylonitrile |
US3914480A (en) * | 1962-12-07 | 1975-10-21 | John L Lang | Process for the preparation of a fly fishing line and the resulting article |
US3216846A (en) * | 1963-01-21 | 1965-11-09 | Gevaert Photo Prod Nv | Process for producing a magnetic recording material |
US3440086A (en) * | 1964-12-23 | 1969-04-22 | Firestone Tire & Rubber Co | Polyurethane precursor-viscosity builder and curing agent coating composition and method of coating therewith |
US3423346A (en) * | 1965-10-19 | 1969-01-21 | Ppg Industries Inc | Latex coating compositions |
US3549407A (en) * | 1968-02-29 | 1970-12-22 | Du Pont | Process for applying a textured decorative coating to a metal substrate and article thereof |
JPS5014664B1 (en) * | 1970-05-12 | 1975-05-29 | ||
US4049747A (en) * | 1971-01-21 | 1977-09-20 | Stauffer Chemical Company | Crosslinked vinyl halide polymers as flame retardant additives for thermoplastics |
US3984492A (en) * | 1973-08-29 | 1976-10-05 | Fuji Photo Film Co., Ltd. | Coating composition for polyester resin |
US4049611A (en) * | 1975-11-19 | 1977-09-20 | Monsanto Company | Modified polyester polyblends and preparation thereof |
US4089911A (en) * | 1976-04-30 | 1978-05-16 | Kao Soap Co., Ltd. | Process for improving the thermal stability of polyurethane-containing resin composition |
US4256852A (en) * | 1978-02-10 | 1981-03-17 | Victor Company Of Japan, Ltd. | Binder composition for magnetic recording tape |
US4350792A (en) * | 1979-03-01 | 1982-09-21 | Stauffer Chemical Company | Blend of internally plasticized vinyl chloride copolymer and polyurethane elastomer |
US4594366A (en) * | 1983-06-29 | 1986-06-10 | Union Carbide Corporation | Connected branched polyols and polyurethanes based thereon |
EP0172993A1 (en) * | 1984-07-30 | 1986-03-05 | DeSOTO, INC. | Low temperature-curing polyester urethane systems |
US4804768A (en) * | 1986-09-30 | 1989-02-14 | Union Carbide Corporation | Process for producing epoxyorganoalkoxysilanes |
US4923735A (en) * | 1987-12-31 | 1990-05-08 | Stamicarbon B.V. | Moulded printed circuit board |
EP0409586A2 (en) * | 1989-07-18 | 1991-01-23 | Tosoh Corporation | Vinyl chloride resin-based composition and packings made therefrom |
EP0409586A3 (en) * | 1989-07-18 | 1992-01-15 | Tosoh Corp | Vinyl chloride resin-based composition and packings made therefrom |
US5360871A (en) * | 1989-07-18 | 1994-11-01 | Tosoh Corporation | Vinyl chloride resin-based composition and packings made therefrom |
US5929153A (en) * | 1994-12-15 | 1999-07-27 | Tosoh Corporation | Vinyl chloride-based polymer-polyurethane composite and method of producing the same |
EP0934983A1 (en) * | 1998-02-04 | 1999-08-11 | Magna Investments N.V. | Polymer compositions |
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